EP0337479B1 - Method for preparation of zeolites - Google Patents
Method for preparation of zeolites Download PDFInfo
- Publication number
- EP0337479B1 EP0337479B1 EP89106708A EP89106708A EP0337479B1 EP 0337479 B1 EP0337479 B1 EP 0337479B1 EP 89106708 A EP89106708 A EP 89106708A EP 89106708 A EP89106708 A EP 89106708A EP 0337479 B1 EP0337479 B1 EP 0337479B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zeolites
- glass
- aqueous medium
- hydrogen fluoride
- fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012736 aqueous medium Substances 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000005388 borosilicate glass Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 239000005337 ground glass Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hexafluorosilicic acid Chemical compound 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
Definitions
- the invention relates to a process for the preparation of zeolites in the presence of hydrogen fluoride.
- zeolites of structure type ZSM-5 can be prepared by heating a reaction mixture of an SiO2 component, Na aluminate, water and tetrapropylammonium oxide to temperatures of 100 to 175 ° C.
- the zeolites obtained can be used as catalysts for the conversion of hydrocarbons.
- EP-A1-0 094 288 discloses the preparation of zeolites of the ZSM-5 structure type, in which gallium oxide or sodium aluminate is reacted with hexafluorosilicic acid in an aqueous medium in the presence of sodium hydroxide; see. Page 10 and page 11 (example 1).
- DE-A1-2 909-929 describes a process for producing a zeolite of the structure type ZSM-5 from SiO2, alkali and an oxide of a trivalent metal in the presence of amines by hydrothermal crystallization, in which glass is used as the starting material . Temperatures between 140 and 160 ° C are preferred.
- the zeolites obtainable by this process can be used, for example, as catalysts in alkylation and isomerization reactions and in the reaction of methanol and / or dimethyl ether or other lower alcohols or ethers in gasoline or olefins.
- the object of the invention is to provide a further process for the production of zeolites.
- a method for producing zeolites from glass containing SiO2, alkali and an oxide of a trivalent metal by crystallization in an aqueous medium is proposed according to the invention, in which the zeolites are crystallized in the presence of hydrogen fluoride.
- the glass used dissolves in the presence of the hydrogen fluoride in the aqueous medium. Whether a solid residue remains on dissolution can depend on how high the selected solids content in the reaction mixture is or how long or how short the hydrogen fluoride is allowed to act on the starting material. A possible solid residue can be filtered off.
- the advantage of carrying out the crystallization of the zeolites in the absence of a solid residue is that zeolites can thus be obtained free of starting material.
- the glass used can be dissolved, for example, at a temperature in the range from 20 to 100 ° C., in particular from 30 to 60 ° C. However, this area is only intended to give the expert a guideline, since one can also work beyond the limit values. It is advantageous to accelerate the dissolution of the glass in the aqueous medium by stirring.
- the formation of the zeolites is a hydrothermal crystallization, which can also be viewed as recrystallization.
- the solution is cooled until crystallization occurs.
- the crystals obtained can be separated from the mother liquor in a manner known per se, washed and dried.
- Gaseous hydrogen fluoride or hydrofluoric acid can be used to prepare the aqueous reaction medium.
- the hydrogen fluoride can also be released from a fluoride, for example with a mineral acid, for example from calcium fluoride with sulfuric acid.
- hydrofluoric acid It is preferred to work with dilute hydrofluoric acid, but it is also possible to use more highly concentrated acids (about a 40 percent acid). The dilution of hydrofluoric acid will find its limits where the reaction rate is no longer satisfactory.
- Finely ground glass is preferably used as the starting material. If borosilicate glass is used, zeolites are obtained whose crystal structure corresponds to that of the aluminosilicate zeolite ZSM-5.
- the loading of the zeolites obtained with, for example, alkali or alkaline earth ions can be exchanged for protons or other cations.
- Finely ground commercial borosilicate glass (containing about 79% by weight SiO2, 12% by weight B2O3, 2.2% by weight Al2O3 and 5% by weight Na2O) was added successively to 100 g of dilute hydrofluoric acid until no glass came off after 5 days. The temperature was kept in the range of 30 to 60 ° C. The solution was then cooled to such an extent that crystals formed. The resulting crystalline product was filtered, washed and dried. An X-ray diffraction analysis - see attached diagram - showed that the well crystalline material corresponded to the structure type of the aluminosilicate zeolite ZSM-5.
- Example 1 was repeated with the only exception that the successive addition of the borosilicate glass was stopped after 3 days. A lower yield of crystalline material (aluminosilicate zeolite ZSM-5) was obtained.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Glass Compositions (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Zeolithen in Gegenwart von Fluorwasserstoff.The invention relates to a process for the preparation of zeolites in the presence of hydrogen fluoride.
Nach der DE-B2-1 767 235 kann man Zeolithe vom Strukturtyp ZSM-5 dadurch herstellen, daß man eine Reaktionsmischung aus einer SiO₂-Komponente, Na-Aluminat, Wasser und Tetrapropylammoniumoxid auf Temperaturen von 100 bis 175 °C erhitzt. Die erhaltenen Zeolithe lassen sich als Katalysatoren für die Umwandlung von Kohlenwasserstoffen verwenden.According to DE-B2-1 767 235, zeolites of structure type ZSM-5 can be prepared by heating a reaction mixture of an SiO₂ component, Na aluminate, water and tetrapropylammonium oxide to temperatures of 100 to 175 ° C. The zeolites obtained can be used as catalysts for the conversion of hydrocarbons.
Aus der EP-A1-0 094 288 ist eine Herstellung von Zeolithen vom Strukturtyp ZSM-5 bekannt, bei dem man in einem wässerigen Medium Galliumoxid oder Natriumaluminat in Gegenwart von Natriumhydroxid mit Hexafluorokieselsäure umsetzt; vgl. Seite 10 und Seite 11 (Beispiel 1).EP-A1-0 094 288 discloses the preparation of zeolites of the ZSM-5 structure type, in which gallium oxide or sodium aluminate is reacted with hexafluorosilicic acid in an aqueous medium in the presence of sodium hydroxide; see.
In der DE-A1-2 909-929 wird ein Verfahren zur Herstellung eines Zeolithen vom Strukturtyp ZSM-5 aus SiO₂, Alkali und einem Oxid eines 3-wertigen Metalls in Gegenwart von Aminen durch hydrothermale Kristallisation beschrieben, bei dem als Ausgangsstoff Glas verwendet wird. Bevorzugt werden Temperaturen zwischen 140 und 160 °C. Die nach diesem Verfahren erhältlichen Zeolithe sind beispielsweise als Katalysatoren bei Alkylierungs- und Isomerisierungsreaktionen sowie bei der Umsetzung von Methanol und/oder Dimethylether oder anderen niederen Alkoholen bzw. Ethern in Benzin oder Olefinen verwendbar.DE-A1-2 909-929 describes a process for producing a zeolite of the structure type ZSM-5 from SiO₂, alkali and an oxide of a trivalent metal in the presence of amines by hydrothermal crystallization, in which glass is used as the starting material . Temperatures between 140 and 160 ° C are preferred. The zeolites obtainable by this process can be used, for example, as catalysts in alkylation and isomerization reactions and in the reaction of methanol and / or dimethyl ether or other lower alcohols or ethers in gasoline or olefins.
Aufgabe der Erfindung ist es, demgegenüber ein weiteres Verfahren zur Herstellung von Zeolithen zur Verfügung zu stellen.In contrast, the object of the invention is to provide a further process for the production of zeolites.
Dazu wird erfindungsgemäß ein Verfahren zur Herstellung von Zeolithen aus Glas mit einem Gehalt an SiO₂, Alkali und einem Oxid eines 3-wertigen Metalls durch Kristallisation in einem wässerigen Medium vorgeschlagen, bei dem man die Zeolithe in Gegenwart von Fluorwasserstoff kristallisiert.For this purpose, a method for producing zeolites from glass containing SiO₂, alkali and an oxide of a trivalent metal by crystallization in an aqueous medium is proposed according to the invention, in which the zeolites are crystallized in the presence of hydrogen fluoride.
Bei dem erfindungsgemäßen Verfahren löst sich das eingesetzte Glas in Gegenwart des Fluorwasserstoffs im wässerigen Medium auf. Ob beim Auflösen ein fester Rückstand zurückbleibt, kann davon abhängen, wie hoch der gewählte Feststoffgehalt im Reaktionsgemisch ist oder wie lange bzw. wie kurz man den Fluorwasserstoff auf das Ausgangsmaterial einwirken läßt. Einen eventuellen festen Rückstand kann man abfiltrieren. Der Vorteil, die Kristallisation der Zeolithe in Abwesenheit eines festen Rückstands durchzuführen, besteht darin, daß sich so Zeolithe frei von Ausgangsmaterial gewinnen lassen.In the process according to the invention, the glass used dissolves in the presence of the hydrogen fluoride in the aqueous medium. Whether a solid residue remains on dissolution can depend on how high the selected solids content in the reaction mixture is or how long or how short the hydrogen fluoride is allowed to act on the starting material. A possible solid residue can be filtered off. The advantage of carrying out the crystallization of the zeolites in the absence of a solid residue is that zeolites can thus be obtained free of starting material.
Man kann das eingesetzte Glas beispielsweise bei einer Temperatur im Bereich von 20 bis 100 °C, insbesondere von 30 bis 60 °C, lösen. Dieser Bereich soll dem Fachmann aber nur Richtwerte geben, da man auch jenseits der Grenzwerte arbeiten kann. Es ist vorteilhaft, das Lösen des Glases im wässerigen Medium durch Rühren zu beschleunigen.The glass used can be dissolved, for example, at a temperature in the range from 20 to 100 ° C., in particular from 30 to 60 ° C. However, this area is only intended to give the expert a guideline, since one can also work beyond the limit values. It is advantageous to accelerate the dissolution of the glass in the aqueous medium by stirring.
Bei der Bildung der Zeolithe handelt es sich um eine hydrothermale Kristallisation, die man auch als Umkristallisation ansehen kann. Zur Bildung der Zeolithe wird die Lösung so weit abgekühlt, bis Kristallisation eintritt. Die anfallenden Kristalle können in an sich bekannter Weise von der Mutterlauge abgetrennt, gewaschen und getrocknet werden.The formation of the zeolites is a hydrothermal crystallization, which can also be viewed as recrystallization. To form the zeolites, the solution is cooled until crystallization occurs. The crystals obtained can be separated from the mother liquor in a manner known per se, washed and dried.
Zur Herstellung des wässerigen Reaktionsmediums kann man gasförmigen Fluorwasserstoff oder Flußsäure verwenden. Der Fluorwasserstoff läßt sich auch aus einem Fluorid freisetzen, etwa mit einer Mineralsäure, beispielsweise aus Calciumfluorid mit Schwefelsäure.Gaseous hydrogen fluoride or hydrofluoric acid can be used to prepare the aqueous reaction medium. The hydrogen fluoride can also be released from a fluoride, for example with a mineral acid, for example from calcium fluoride with sulfuric acid.
Vorzugsweise arbeitet man mit verdünnter Fluorwasserstoffsäure, es sind jedoch auch höher konzentrierte Säuren verwendbar (etwa eine 40-proz. Säure). Das Verdünnen der Fluorwasserstoffsäure wird dort seine Grenzen finden, wo die Reaktionsgeschwindigkeit nicht mehr befriedigt.It is preferred to work with dilute hydrofluoric acid, but it is also possible to use more highly concentrated acids (about a 40 percent acid). The dilution of hydrofluoric acid will find its limits where the reaction rate is no longer satisfactory.
Vorzugsweise verwendet man feingemahlenes Glas als Ausgangsmaterial. Wenn man Borsilikatglas einsetzt, erhält man Zeolithe, deren Kristallstruktur der des Aluminosilikatzeolithen ZSM-5 entspricht.Finely ground glass is preferably used as the starting material. If borosilicate glass is used, zeolites are obtained whose crystal structure corresponds to that of the aluminosilicate zeolite ZSM-5.
Mit Hilfe bekannter Ionenaustauschtechniken läßt sich die Beladung der erhaltenen Zeolithe mit beispielweise Alkali- oder Erdalkaliionen gegen Protonen oder andere Kationen austauschen.With the help of known ion exchange techniques, the loading of the zeolites obtained with, for example, alkali or alkaline earth ions can be exchanged for protons or other cations.
Nachstehend wird die Erfindung durch Beispiele näher erläutert.The invention is explained in more detail below by examples.
Es wurde feingemahlenes handelsübliches Borsilikatglas (mit einem Gehalt an etwa 79 Gew.-% SiO₂, 12 Gew.-% B₂O₃, 2,2 Gew.-% Al₂O₃ und 5 Gew.-% Na₂O) sukzessiv in 100 g verdünnter Flußsäure gegeben, bis sich nach 5 Tagen kein Glas mehr löste. Die Temperatur wurde im Bereich von 30 bis 60 °C gehalten. Danach wurde die Lösung soweit abgekühlt, daß sich Kristalle bildeten. Das angefallene kristalline Produkt wurde filtriert, gewaschen und getrocknet. Eine Röntgenbeugungsanalyse - vergleiche beiliegendes Diagramm - ergab, daß das gut kristalline Material dem Strukturtyp des Aluminosilikatzeolithen ZSM-5 entsprach.Finely ground commercial borosilicate glass (containing about 79% by weight SiO₂, 12% by weight B₂O₃, 2.2% by weight Al₂O₃ and 5% by weight Na₂O) was added successively to 100 g of dilute hydrofluoric acid until no glass came off after 5 days. The temperature was kept in the range of 30 to 60 ° C. The solution was then cooled to such an extent that crystals formed. The resulting crystalline product was filtered, washed and dried. An X-ray diffraction analysis - see attached diagram - showed that the well crystalline material corresponded to the structure type of the aluminosilicate zeolite ZSM-5.
Es wurde Beispiel 1 mit der einzigen Ausnahme wiederholt, daß die sukzessive Zugabe des Borsilikatglases nach 3 Tagen abgebrochen wurde. Es wurde eine geringere Ausbeute kristallines Material (Aluminosilikatzeolith ZSM-5) erhalten.Example 1 was repeated with the only exception that the successive addition of the borosilicate glass was stopped after 3 days. A lower yield of crystalline material (aluminosilicate zeolite ZSM-5) was obtained.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT89106708T ATE78239T1 (en) | 1988-04-15 | 1989-04-14 | PROCESS FOR THE PRODUCTION OF ZEOLITES. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3812592 | 1988-04-15 | ||
| DE3812592A DE3812592A1 (en) | 1988-04-15 | 1988-04-15 | METHOD FOR PRODUCING ZEOLITES |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0337479A2 EP0337479A2 (en) | 1989-10-18 |
| EP0337479A3 EP0337479A3 (en) | 1991-01-23 |
| EP0337479B1 true EP0337479B1 (en) | 1992-07-15 |
Family
ID=6352081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89106708A Expired - Lifetime EP0337479B1 (en) | 1988-04-15 | 1989-04-14 | Method for preparation of zeolites |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0337479B1 (en) |
| JP (1) | JPH029710A (en) |
| AT (1) | ATE78239T1 (en) |
| DE (2) | DE3812592A1 (en) |
| ZA (1) | ZA892744B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6849248B2 (en) | 2001-05-14 | 2005-02-01 | Consejo Superior De Investigaciones Cientificas | Porous crystalline material (zeolite ITQ-21), the preparation method thereof and use of same in the catalytic conversion of organic compounds |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2671069B1 (en) * | 1990-12-27 | 1993-04-09 | Inst Francais Du Petrole | MFI TYPE ZEOLITE AND PROCESS FOR PREPARING THE SAME. |
| ATE143652T1 (en) * | 1991-11-20 | 1996-10-15 | Dow Chemical Co | METHOD FOR GROWING CRYSTALLINE, MICROPOROUS SOLIDS IN A FLUORDIC, ESSENTIALLY NON-AQUEOUS GROWTH MEDIUM |
| ES2204257B1 (en) | 2001-11-30 | 2005-05-01 | Universidad Politecnica De Valencia | SYNTHESIS OF ITQ-21 IN THE ABSENCE OF FLUORIDE IONS. |
| ES2228278B1 (en) | 2003-09-29 | 2006-06-01 | Universidad Politecnica De Valencia. | MICROPOROUS CRYSTAL MATERIAL OF NATURE ZEOLITICA (ZEOLITA ITQ-28). |
| ES2245588B1 (en) | 2004-03-11 | 2007-08-16 | Universidad Politecnica De Valencia | MICROPOROUS CRYSTAL MATERIAL OF ZEOLITIC NATURE WITH LTA STRUCTURE (ITQ-29), ITS PREPARATION PROCEDURE AND USES OF THE SAME IN PROCESSES OF TRANSFORMATION AND SEPARATION OF ORGANIC COMPOUNDS. |
| WO2006037437A1 (en) | 2004-10-01 | 2006-04-13 | Exxonmobil Chemical Patents Inc. | Aluminophosphate molecular sieve, its synthesis and use |
| JP4990145B2 (en) | 2004-10-01 | 2012-08-01 | エクソンモービル・ケミカル・パテンツ・インク | Aluminophosphate molecular sieve, its synthesis and use |
| ES2284379B1 (en) | 2006-02-28 | 2008-11-01 | Universidad Politecnica De Valencia | A MICROPOROUS CRYSTAL MATERIAL, ZEOLITA ITQ-37, PREPARATION AND USE PROCEDURE. |
| WO2008035374A2 (en) * | 2006-07-21 | 2008-03-27 | Bharat Petroleum Corporation Limited | Microporous crystalline silicoalumino/(metallo) aluminophosphate molecular sieve and method of synthesis thereof |
| ES2303787B2 (en) | 2007-02-01 | 2009-06-12 | Universidad Politecnica De Valencia | "MICROPOROUS CRYSTAL MATERIAL OF ZEOLITIC NATURE, ZEOLITA ITQ-39, PREPARATION PROCEDURE AND USES". |
| JP5646807B2 (en) * | 2008-03-21 | 2014-12-24 | 株式会社ゼオライト・アーティフィシャル | Method for producing artificial zeolite |
| ES2554648B1 (en) | 2014-06-20 | 2016-09-08 | Consejo Superior De Investigaciones Científicas (Csic) | ITQ-55 material, preparation and use procedure |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3411874A (en) * | 1964-11-09 | 1968-11-19 | Mobil Oil Corp | Zsm-2 zeolite and preparation thereof |
| US3586479A (en) * | 1968-09-23 | 1971-06-22 | Bayer Ag | Production of synthetic faujasite |
| DE2909929A1 (en) * | 1979-03-14 | 1980-09-25 | Basf Ag | METHOD FOR PRODUCING A ZSM-5 STRUCTURAL TYPE |
| DE3202657A1 (en) * | 1982-01-28 | 1983-08-04 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING CATALYTICALLY ACTIVE ALUMOSILICATES AND THEIR USE |
| FR2526780A1 (en) * | 1982-05-11 | 1983-11-18 | Rhone Poulenc Spec Chim | PROCESS FOR PRODUCING ZEOLITES |
-
1988
- 1988-04-15 DE DE3812592A patent/DE3812592A1/en active Granted
-
1989
- 1989-04-14 AT AT89106708T patent/ATE78239T1/en not_active IP Right Cessation
- 1989-04-14 EP EP89106708A patent/EP0337479B1/en not_active Expired - Lifetime
- 1989-04-14 JP JP1096211A patent/JPH029710A/en active Pending
- 1989-04-14 DE DE8989106708T patent/DE58901829D1/en not_active Expired - Lifetime
- 1989-04-14 ZA ZA892744A patent/ZA892744B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6849248B2 (en) | 2001-05-14 | 2005-02-01 | Consejo Superior De Investigaciones Cientificas | Porous crystalline material (zeolite ITQ-21), the preparation method thereof and use of same in the catalytic conversion of organic compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0337479A3 (en) | 1991-01-23 |
| EP0337479A2 (en) | 1989-10-18 |
| ZA892744B (en) | 1989-12-27 |
| DE3812592A1 (en) | 1989-10-26 |
| JPH029710A (en) | 1990-01-12 |
| DE3812592C2 (en) | 1991-08-29 |
| ATE78239T1 (en) | 1992-08-15 |
| DE58901829D1 (en) | 1992-08-20 |
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